Integrated process for the preparation of olefin oxides

ABSTRACT

The present invention relates to an integrated process for the preparation in continuous of epoxides which comprises: (a) preparing an alcoholic or hydro-alcoholic solution of hydrogen peroxide in a concentration of over 3% by weight, using a gaseous stream containing hydrogen, oxygen and an inert gas, in the presence of a bimetallic catalyst based on palladium and platinum as active components; (b) putting the alcoholic or hydro-alcoholic solution of hydrogen peroxide obtained in step (a) in contact with an olefin and a buffering agent, in the presence of an epoxidation catalyst suspended in the reaction solvent, in order to obtain a reaction mixture containing the epoxide corresponding to the olefin, water and alcoholic solvent; (c) treating the alcoholic stream leaving step (b), after separation of the epoxide, in order to eliminate the nitrogenated compounds present; (d) feeding the alcoholic solvent obtained in (c) to step (a). The process may comprise a further step (e), wherein the raw hydro-alcoholic mixture of the flash column bottom, is used, when necessary, for diluting the alcoholic or hydro-alcoholic solution of hydrogen peroxide obtained in step (a) to the value required by the epoxidation plant. The process operates under high safety conditions and with a high overall efficiency, in terms of productivity and selectivity.

The present invention relates to an integrated process for thepreparation in continuous of epoxides by the direct oxidation of anolefin with hydrogen peroxide.

More specifically, the present invention relates to an integratedprocess for the preparation in continuous of propylene oxide consistingin the production of an alcoholic or hydro-alcoholic solution ofhydrogen peroxide by the reaction between hydrogen and oxygen in thepresence of a bimetallic catalyst based on palladium or platinum asactive components, feeding said solution to an epoxidation process ofpropylene in the presence of an epoxidation catalyst, and feeding therecycled alcoholic solvent leaving the epoxidation plant, suitablypretreated, to the hydrogen peroxide production plant. The process maycomprise a further step (e), in which the raw hydro-alcoholic mixture ofthe flash column bottom, is used, when necessary, for diluting thealcoholic or hydro-alcoholic solution of hydrogen peroxide obtained instep (a) to the value required by the epoxidation plant.

Epoxides, or olefin oxides, are intermediates which can be used for thepreparation of a wide variety of compounds. For example, epoxides can beused for the production of glycols, condensation polymers such aspolyesters or for the preparation of intermediates used in the synthesisof polyurethane foams, elastomers, seals and similar products.

Current technologies adopted on an industrial scale for the productionof propylene oxide (PO) are based on processes via chlorohydrin andprocesses via indirect oxidation with hydroperoxides as oxygen source.

In particular, the commercialized chlorohydrin process involves thesynthesis of propylene chlorohydrin (PCH) and subsequentdehydrohalogenation of PCH to propylene oxide (PO).

This process however has the following disadvantages:

-   -   the production of high quantities of aqueous effluents (40-60        Kg/kg of PO) containing sodium or calcium chlorides;    -   the coproduction of chlorinated organic products which,        depending on their end-use, must undergo suitable treatment.

Processes via oxidation preferably use ter butyl hydroperoxide andethylbenzene hydroperoxide as hydroperoxides.

These processes cause the formation of a higher quantity of co-productsof commercial interest with respect to PO. For example, the process viater butyl hydroperoxide co-produces 2.5-3.5 Kg of ter butyl alcohol perKg of PO, whereas that via ethylbenzene hydroperoxide co-produces2.2-2.5 Kg of styrene per Kg of PO.

The presence of these co-products can be of little advantage if therequest for PO and the respective co-products is not suitably balanced.For example, when the demand for styrene or MTBE, obtained from terbutyl alcohol, is high, the economics of this process are competitivewith those of the process via chlorohydrin, otherwise these processesare not economic.

Other synthetic techniques for the indirect oxidation of propyleneinvolve the use of hydrogen peroxide and essentially consist in:

-   1) synthesis of hydrogen peroxide; and-   2) its use in the epoxidation process of propylene to propylene    oxide.

Aqueous solutions of H₂O₂ are typically obtained industrially by meansof a complex two-step process. In this process a solution ofanthraquinone, such as butylanthraquinone or ethylanthraquinone, in anorganic medium immiscible with water, is first hydrogenated and thenoxidized with air to produce H₂O₂ which is subsequently extracted inaqueous phase. This process is onerous due to the high costs derivingfrom the investment necessary for setting up the complex productionunit, the necessity of separating and disposing of the by-productsgenerated during the oxidation phase, and purifying and reintegratingthe anthraquinone solution before its re-use.

A second method for the production of hydrogen peroxide comprises theuse of secondary alcohols such as isopropanol and methylbenzylalcohol(U.S. Pat. No. 2,871,102, EP-378,388) or high-boiling secondary alcoholssuch as diaryl methanol (U.S. Pat. No. 4,303,632) with oxygen.

These known processes, however, substantially suffer from disadvantagesderiving from the necessity of operating at high reaction temperatures(generally ranging from 100 to 180° C.), the partial oxidation of theketone which is formed as main co-product, the necessity of using ahydrogen peroxide stabilizer (orthophosphoric acid or sodiumpyrophosphate).

Furthermore, these processes are complicated by the necessity ofseparating and recovering the ketone and by-products from the reactionmixture before using the hydrogen peroxide solution in a subsequentepoxidation process.

Another method for the production of hydrogen peroxide, which seemsattractive from a technical and economic point of view, is based on thedirect synthesis of hydrogen peroxide from H₂ and O₂.

These processes generally use a catalytic system consisting of a noblemetal, particularly metals of the platinum group or their mixtures, inthe form of salts or as supported metals, by reacting the two gases in asolvent consisting of an aqueous medium or an aqueous-organic medium.

The industrial embodiment of these processes however has proved to bedifficult for the following reasons:

-   A) the use of mixtures of H₂ and O₂ in concentrations falling within    the explosivity range, as the mixture becomes explosive when the    concentration of H₂ exceeds a value which, in relation to the    pressure and concentration of O₂, varies from 4.5 to 6% by volume;-   B) even when operating outside the explosivity range of H₂—O₂    mixtures, the use of high concentrations of O₂ is risky to handle    and has a limited compatibility with the presence of flammable    organic solvent mediums;-   C) the use in the reaction medium of high concentrations of    promoters, for example acid promoters, halogenated products and/or    other additives, makes the catalytic system or H₂O₂ solution    unstable. This makes it necessary to add stabilizers, with onerous    purification operations of the H₂O₂ solution before its use;-   D) low productivity and selectivity of the reaction and the    production of H₂O₂ solutions which are too dilute for economic    industrial exploitation;-   E) poor stability of the catalytic system under the reaction    conditions.

Patent application EP-812836, for example, describes a process for thepreparation of propylene oxide which consists in reacting hydrogen andoxygen in the presence of a catalytic system based on supportedpalladium, in a hydro-alcoholic medium and using the hydro-alcoholicmixture of hydrogen peroxide thus obtained in the epoxidation process.

The illustrative examples of this document describe the production ofhydro-alcoholic solutions containing H₂O₂ in concentrations ranging from0.15 to 0.39% by weight. Using these solutions in the subsequentepoxidation reaction, after 1 hour, hydrogen peroxide conversions equalto 99% and 65% respectively, are obtained, with a selectivity topropylene oxide ranging from 70% to 95%, i.e. with a maximum yield to POof 70%.

This process does not seem to be of industrial interest for thefollowing reasons:

-   A) The use, in the reaction medium for the production of hydrogen    peroxide, of high concentrations of promoters, for example acid    promoters, halogenated products and/or other additives, makes it    necessary to add considerable quantities of neutralizers before its    use in the subsequent epoxidation process;-   B) overall low process concentration, productivity and selectivity.    This requires the use of high reaction volumes in both steps of the    integrated process;-   C) Production of a high stream of waste products to be disposed of    in the epoxidation process;-   D) The use of diluted hydro-alcoholic solutions of hydrogen peroxide    implies the production of a stream of alcoholic distillate whose    entity makes the process rather un-economic.

The Applicant has now found that by using a well defined group ofmetallic catalysts and operating conditions in the initial reactionbetween hydrogen and oxygen, by suitably treating the recycled alcoholicsolvent leaving the epoxidation plant before being fed to the hydrogenperoxide production plant, and by using the raw hydro-alcoholic mixtureof the flash column bottom, when necessary, to dilute thehydro-alcoholic solution of hydrogen peroxide obtained in step (a) tothe value required by the epoxidation plant, an overall high processefficiency is obtained in terms of productivity and selectivity.

In particular, when operating according to the process of the presentinvention, the following advantages are obtained:

-   -   reduction in waste products in the epoxidation plant;    -   reduction in the volume of solvent to be distilled in the        epoxidation reaction plant;    -   high stability of the catalysts used in the two reactions;    -   reduction in the reaction volumes;    -   high degree of purity of the epoxides.

In accordance with this, the objective of the present invention relatesto an integrated process for the preparation in continuous of epoxidesby the direct oxidation of an olefin with hydrogen peroxide whichcomprises:

-   (a) preparing an alcoholic or hydro-alcoholic solution of hydrogen    peroxide in a concentration of over 3% by weight, using a gaseous    stream containing hydrogen, oxygen and an inert gas, in the presence    of a bimetallic catalyst based on palladium and platinum as active    components;-   (b) putting the alcoholic or hydro-alcoholic solution of hydrogen    peroxide obtained in step (a) in contact with an olefin and a    buffering agent, in the presence of an epoxidation catalyst    suspended in the reaction solvent, in order to obtain a reaction    mixture containing the epoxide corresponding to the olefin, water    and the alcoholic solvent;-   (c) treating the alcoholic stream leaving step (b), after separation    of the epoxide, in order to eliminate the nitrogenated compounds    present;-   (d) feeding the alcoholic solvent obtained in (c) to step (a).

The process may comprise a further step (e), wherein the rawhydro-alcoholic mixture of the flash column bottom, is used, whennecessary, for diluting the hydro-alcoholic solution of hydrogenperoxide obtained in step (a) to the value required by the epoxidationplant. This advantageously allows a reduction in the volume of solventto be distilled in the epoxidation reaction plant.

The process for the preparation of epoxides according to the presentinvention can be described in detail as follows.

In the first step, the process for the synthesis of epoxides comprises:

-   (a) feeding to a reactor, containing a catalyst based on palladium    and platinum, heterogeneous and kept in dispersion in a liquid    reaction medium:-   (i) a liquid stream consisting of an alcohol or an alcohol-water    mixture with a prevalent alcoholic content, containing an acid    promoter and a halogenated promoter.-   (ii) a gaseous stream containing hydrogen, oxygen and an inert gas,    characterized in that the concentration of hydrogen is lower than    4.5% by volume and the concentration of oxygen is lower than 21% by    volume, the complement to 100 being an inert gas;-   (b) removing from the reactor:-   (iii) a liquid stream essentially consisting of the stream (i) and    also containing the hydrogen peroxide and water produced by the    reaction, characterized in that the concentration of hydrogen    peroxide is higher than 3% by weight; and-   (iv) a gaseous stream essentially consisting of non-reacted hydrogen    and oxygen and the inert gas.

The reactor used can be any reactor suitable for operating in continuousand conducting the reaction in a triphasic system such as thatdescribed, obtaining an effective contact between the gaseous phase,liquid phase and catalyst kept in dispersion (so-called slurry system).For example, stirred reactors, bubble reactors, gas-lift reactors withinternal or external circulation, such as those described in the stateof the art, are suitable for the purpose.

The reactor is maintained under appropriate temperature and pressureconditions. According to the process, object of the invention, thetemperature normally ranges from −10° C. to 60° C., preferably from 0°C. to 40° C. The pressure normally ranges from 1 to 300 bars, preferablyfrom 40 to 150 bars.

The residence time of the liquid medium in the reactor normally rangesfrom 0.05 to 5 hours, preferably from 0.10 to 2 hours.

The catalyst which can be used for the purposes of the invention is aheterogeneous catalyst containing palladium and platinum as activecomponents.

In these catalysts, the palladium is normally present in a quantityranging from 0.1 to 3% by weight and the platinum in a quantity rangingfrom 0.01 to 1% by weight, with an atomic ratio between platinum andpalladium ranging from 1/500 to 100/100.

The palladium is preferably present in a quantity ranging from 0.4 to 2%by weight and the platinum in a quantity ranging from 0.02 to 0.5% byweight, with an atomic ratio between platinum and palladium ranging from1/200 to 20/100.

In addition to palladium and platinum, other metals of group VIII or IB,such as, for example, ruthenium, rhodium, iridium and gold, can bepresent as active components or promoters, in a concentration generallynot higher than that of the palladium.

The catalyst can be prepared by dispersing the active components on aninert carrier by means of precipitation and/or impregnation startingfrom precursors consisting, for example, of solutions of their salts orsoluble complexes, and therein reduced to the metal state by means ofthermal and/or chemical treatment with reducing substances such ashydrogen, sodium formiate, sodium citrate by means of preparativetechniques well known in the state of the art.

The inert carrier may typically consist of silica, alumina,silica-alumina, zeolites, activated carbon, and other materials wellknown in the state of the art. Activated carbon is preferred for thepreparation of the catalysts useful for the invention.

Activated carbons which can be used for the invention are selected fromthose of fossil or natural origin deriving for example from wood,lignite, peat or coconut and having a surface area higher than 300 m²/gand which can reach 1400 m²/g, in particular those having a surface areahigher than 600 m²/g.

Preferred activated carbons are those with a low ash content.

The sulfonated activated carbons described in Italian patent applicationMI 98A01843 can be used for the purpose.

Before the supporting or impregnation of the metals, the activatedcarbon can be subjected to treatment such as washing with distilledwater or treatment with acids, bases or diluted oxidizing agents, forexample acetic acid, hydrochloric acid, sodium carbonate and hydrogenperoxide.

The catalyst is normally suspended in the reaction medium at aconcentration ranging from 0.1 to 10% by weight, preferably from 0.3 to3% by weight.

The liquid stream (i) consists of an alcohol or a mixture of C₁-C₄alcohols or a mixture of said alcohols with water with a prevalentalcoholic content. A mixture with a prevalent alcoholic content refersto a mixture containing over 50% by weight of alcohol or mixture ofalcohols. Among C₁-C₄ alcohols, methanol is preferred for the purposesof the invention. Among preferred mixtures is a mixture of methanol andwater containing at least 70% by weight of methanol.

The liquid stream also contains an acid promoter and a halogenatedpromoter.

The acid promoter can be any substance capable of generating H⁺ hydrogenions in the reaction liquid medium and is generally selected frominorganic acids such as sulfuric, phosphoric, nitric acid or fromorganic acids such as sulfonic acids.

Sulfuric acid and phosphoric acid are preferred. The concentration ofthe acid generally ranges from 0 to 1000 mg per kg of liquid medium andpreferably from 10 to 500 mg per kg of liquid medium.

The halogenated promoter can be any substance capable of generatinghalide ions in the reaction liquid medium. Substances capable ofgenerating bromide ions are preferred. These substances are generallyselected from hydrobromic acid and its salts soluble in the reactionmedium, for example alkaline bromides, hydrobromic acid being preferred.

The concentration of halogenated promoter generally ranges from 0.1 to50 mg per kg of liquid medium and preferably from 1 to 10 mg per kg ofliquid medium.

The gaseous stream (ii) at the inlet contains a concentration ofhydrogen of less than 4.5% by volume and a concentration of oxygen ofless than 21% by volume, the complement to 100 being an inert gas, whichis generally selected from nitrogen, helium, argon. Said gas ispreferably nitrogen.

In the gaseous stream (ii) the concentration of hydrogen preferablyranges from 2% to 4% by volume and the concentration of oxygenpreferably ranges from 6% to 18% by volume.

The oxygen can be supplied to said stream using pure or substantiallypure oxygen, or enriched air, as raw material, containing for examplefrom 21 to 90% of oxygen or air, the composition of the stream thenbeing brought to the desired values, defined above, by the addition of asuitable concentration of inert gas.

The liquid stream (iii) leaving the reactor normally has a concentrationof hydrogen peroxide of over 3% by weight and, preferably from 4% to 10%by weight. It also contains the acid promoter and halogenated promoterin quantities equal to those charged with the liquid stream fed andwater in a quantity equal to that charged with the liquid stream fedtogether with the water obtained as reaction by-product. The latterusually represents an additional concentration of 0.5% to 2.5% byweight.

The liquid stream (iii) is separated from the catalyst by means offiltration techniques well known in the state of the art, for example bythe use of filters situated inside the reactor or in a specialrecirculation cycle of the reaction mixture outside the reactor. In thelatter case, the tangential filtration technique can also beconveniently adopted.

The liquid stream (iii) proves to be stable to storage without requiringthe addition of stabilizing substances.

The gaseous stream (iv) leaving the reactor, essentially consisting ofnon-reacted hydrogen and oxygen and the inert gas, generally contains avolume concentration of hydrogen equal to or lower than 2%, normallyranging from 0.5 to 1.5%, and a volume concentration of oxygen generallyless than 18%, normally ranging from 6 to 12%.

In an embodiment of the process of the present invention, the gaseousstream leaving the reactor is recycled to the feeding to the reactor,after flushing from the system the fraction necessary for eliminatingthe quantity of inert gas charged in excess with the feeding,particularly when air is used as oxygen source. In this case, thegaseous stream (ii) fed to the reactor consists of the recycled fractionof the above stream (iv), containing a quantity of hydrogen and oxygen(as such or in the form of air or enriched air) essentially equal tothat used up by the reaction and that used for the flushing.

According to another embodiment of the process of the present invention,the gaseous stream (iv) leaving the reactor is fed to one or moresubsequent reactors operating analogously to that described above, afteradding each time a quantity of hydrogen and oxygen (as such or in theform of air or enriched air) essentially equal to that used up by thereaction which takes place in the single reactors.

Operating under the conditions described above, it is possible toproduce hydrogen peroxide under safety conditions with a reactionproductivity normally ranging from 30 to 200 g of H₂O₂ (expressed asH₂O₂ at 100%) per liter of reaction medium per hour and with a molarselectivity towards the formation of H₂O₂, referring to the hydrogenused up, generally higher than 70%.

Furthermore, the possibility of minimizing the concentrations of acidand halogenated promoters present in the reaction liquid mediumpositively influences the stability of the catalytic system; there areno signs of a substantial loss in the catalytic activity after 1000hours of reaction in continuous.

The filtered liquid stream (iii) is fed to a reaction unit consisting ofone or more reactors containing the epoxidation catalyst suspended inthe reaction solvent together with the olefin and a buffering agent.

When the concentration of hydrogen peroxide in the liquid stream (iii)is higher than the values required by the epoxidation process(3.5-4.5%), the liquid stream (iii) is diluted with the rawhydro-alcoholic mixture of the flash column bottom to the value requiredby the epoxidation plant.

The filtered liquid product leaving the reaction unit is fed to adistillation unit consisting of one or more stripping (flash) columns,one for each reactor of the reaction unit, to obtain a product at thehead essentially consisting of olefin oxide and non-reacted olefin and aproduct at the bottom essentially consisting of solvent, non-reactedhydrogen peroxide, water and reaction by-products. The product at thebottom of the distillation unit is fed, for the quota not recycled tothe epoxidation reaction unit, to a decomposition unit R4 consisting ofone or more reactors containing a decomposition catalyst having thefunction of decomposing the residual hydrogen peroxide into O₂ and H₂O.

The mixture leaving the decomposition unit R4, essentially consisting ofsolvent, oxygen and water, is fed, together with an inert gas(preferably nitrogen), to a phase separator V4 to obtain, at the head, agaseous phase containing oxygen, inert gas and traces of solvent and, atthe bottom, a liquid phase consisting of solvent, water and reactionby-products.

The gaseous phase leaving V4 is fed to a condensation system consistingof one or more condensers in series for the recovery of the residualsolvent, whereas the non-condensable compounds (oxygen and inert gaswith traces of solvent) are discharged.

The solvent leaving the condensation system and the liquid phase leavingR4 are fed to the distillation column C6-A together with a dilutedaqueous or hydro-alcoholic solution containing sulfuric acid (about10-50 mg/kg of sulfuric acid with respect to the total stream) toobtain, at the head, the purified solvent containing traces of lightproducts and a product, at the bottom, essentially consisting ofreaction water and that charged with the hydrogen peroxide, reactionby-products and traces of solvent, which is discharged.

The solvent leaving the condensation system and the liquid phase leavingV4 are preferably fed towards the bottom of the distillation columnC6-A, whereas the acid solution is fed at a height equal to about ⅔ ofthe column. The function of this acid treatment is to completelyseparate the nitrogenated basic products present in the stream, whichcould influence the performance of the catalyst used for the synthesisof hydrogen peroxide. The solvent leaving the head of the column C6-A isfed to a column C6-B, in order to separate the light products at thehead, whereas the purified solvent is separated at the bottom.

The stream at the head of the column C6-B is sent to a distillationcolumn C6-C, to recover, at the bottom, the solvent without lightproducts, recycled to the hydrogen peroxide synthesis reaction, and aconcentrated stream of light products, at the head.

The acid treatment in the column described above, can be substituted bymeans of treatment on the methanol at the head of C6-A with activatedcarbon, sulfonic resins or sulfonated carbons (Italian PatentApplication MI 98A01843).

The product at the head of the stripping column(s) and the vent productsof the reactors are fed to a distillation column C4 to obtain a product,at the head, consisting of non-reacted olefin, recycled to the reactionunit, and a product, at the bottom essentially consisting of olefinoxide.

The product at the bottom of the distillation column is fed to apurification system C5. The residual olefin obtained at the head. C5 isrecycled to the reaction unit, the liquid phase, at the bottom,essentially consisting of solvent is recycled to the flash column(s),and the olefin oxide with a commercial purity is obtained from a lateralcut in the upper part of the column.

Olefins which can be used in the process of the present invention arethose having general formula (I)

wherein: R₁, R₂, R₃ and R₄, the same or different, can be hydrogen, analkyl radical with from 1 to 20 carbon atoms, an aryl radical, alkylarylradical with from 7 to 20 carbon atoms, a cyclo-alkyl radical with from6 to 10 carbon atoms, an alkylcyclo-alkyl radical with from 7 to 20carbon atoms.

The radicals R₁, R₂, R₃ and R₄, can form, in pairs, saturated orunsaturated rings. Furthermore, said radicals can contain halogen atoms,nitro, nitrile, sulfonic and relative ester groups, carbonyl, hydroxyl,carboxyl, thiol, amine and ether groups.

The olefins can carry the above substituents both on unsaturated carbonatoms and in different positions.

Non-limiting examples of olefins having formula (I) are: ethylene,propylene, allyl chloride, allyl alcohol, butenes, pentenes, hexenes,heptenes, octene-1, 1-tridecene, mesityl oxide, isoprene, cyclo-octene,cyclo-hexene or bicyclic compounds such as norbornenes, pinenes, etc.

The preferred olefin is propylene. Propylene with a purity of over 70%is generally used. The propylene is preferably available as a streamfrom steam cracking with a minimum purity of 96%, the remainingpercentage consisting of propane and typical C₃ impurities.

The quantity of hydrogen peroxide with respect to the olefin is notcritical, but a molar ratio olefin/H₂O₂ ranging from 10:1 to 1:10,preferably from 6:1 to 1:1, is preferably used.

The epoxidation reaction can be carried out in one or more liquidsolvents at epoxidation temperatures, compatible with hydrogen peroxideand capable of dissolving the olefin and olefin oxide produced.

Solvents of a polar nature consisting of an alcohol or mixture of C₁-C₄alcohols or a mixture of said alcohols with water with a prevalentalcoholic content, are typically used. A mixture with a prevalentalcoholic content refers to a mixture containing over 50% by weight ofalcohol or mixture of alcohols. Among C₁-C₄ alcohols, methanol ispreferred for the. purposes of the invention. Among the mixtures, amixture of methanol and water containing at least 70% by weight ofmethanol, is preferred.

The buffering agent is selected from ammonia, ammonium acetate, ammoniumformiate or a system consisting of a nitrogenated base and one of itssalts with an organic or inorganic acid as described in Italian patentapplication MI 99A/001658.

The buffering agent is fed in continuous with one of the reagentsstreams fed to the epoxidation reactor, in such a quantity as tomaintain the pH of the reaction mixture, measured under the operatingconditions, at a value higher than 5, preferably ranging from 5.5 to 8.

The epoxidation catalyst which can be used in the process of the presentinvention is selected from those generally known under the name oftitanium silicalites.

For example, titanium-silicalites can be used, with an MFI structure,described in the patent U.S. Pat. No. 4,410,501, which also describestheir structural characteristics.

Titanium silicalites in which part of the titanium is substituted byother metals such as boron, aluminum, iron or gallium, can also be used.These substituted titanium silicalites and the methods for theirpreparation are described in European patent applications 226,257,226,258 and 266,825.

Titanium silicalites with a MEL or intermediate MFI/MEL structure,described in Belgian patent 1,001,038, can also be used. Othertitanium-silicalites can be selected from beta zeolites containingtitanium and having a BEA structure, described in Spanish patent2,037,596, ZSM-12 containing titanium and optionally aluminum, describedin “Journal of Chemical Communications, 1992, page 745”.

The preferred catalyst according to the present invention istitanium-silicalite having general formula (II):xTiO₂·(1−x)SiO₂wherein: x represents a number ranging from 0.0001 to 0.04, preferablythe value of x ranges from 0.01 to 0.025, and described, for example inpatents U.S. Pat. Nos. 4.410,501, 4,824,976, 4,666,692, 4,656,016,4,859,785, 4,937,216.

The catalyst can be used in the form of powder, pellets, microspheres,extruded or other convenient physical forms.

The use of a ligand (co.gel) or an inert carrier combined with thecatalyst can be advantageous. Supported catalysts can be prepared usingknown methods.

The inert carrier may typically consist of silica, alumina,silica-alumina, zeolites, activated carbon, and other materials wellknown in the state of the art.

The quantity of catalyst used in the process of the present invention isnot critical; it is selected however so as to allow epoxidation reactionto be completed in the shortest possible time.

The quantity of catalyst is generally selected in relation to thevarious parameters, such as the reaction temperature, reactivity andconcentration of the olefin, the concentration of hydrogen peroxide,type and composition of the solvent, catalytic activity and type ofreactor or reaction system used.

The quantity of catalyst typically ranges from 1 to 15% by weight withrespect to the reaction mixture, preferably from 4 to 10% by weight. 10The temperature used in the process of the present invention generallyranges from 20 to 150° C., preferably from 40 to 100° C., from 55 to 90°C. is particularly preferred.

The operating pressure is such as to allow the olefin to be maintainedin liquid phase at the temperature pre-selected for the reaction. Ingeneral, the operating pressure is higher than atmospheric pressure whengaseous olefins are used.

The reactor used in the epoxidation reaction can be any reactor suitablefor operating in continuous and conducting the reaction in a system suchas that described, obtaining an effective contact between the olefin,the liquid phase and catalyst kept in suspension.

For example, stirred reactors, bubble reactors, gas-lift reactors withinternal or external circulation or CSTR (Continuous Stirred TankReactors) or PFR (Plug Flow Reactors), as described in the state of theart, are suitable for the purpose.

The olefin charged, this term referring to fresh olefin, recycled olefinor their mixtures, is fed to the reaction step under flow-rate controland in excess to maximize the conversion and selectivity to olefin oxideand maintain the reaction pressure. A mixture consisting of fresh olefinderiving from battery limits and recycled olefin is preferably fed.Before entering the reaction unit, the fresh olefin can be purified inthe distillation column C4.

According to an embodiment of the process of the present invention, thereaction unit is made up of three reactors R1-R2-R3 of the CSTR type andisotherms.

The reactors R1 and R2 operate under substantially identical conditions,i.e. at a temperature of about 55-75° C. and a pressure of 13 bars,whereas the reactor R3, which acts as finishing reactor, i.e. withexhaustion of the hydrogen peroxide fed to the reactors R1 and R2,operates at a temperature of 79-90° C. and a pressure of 8 bars.

The overall oxidation reaction of the olefin is carried out in such away as to have a concentration of H₂O₂ of less than 100 ppm in thestream leaving the unit R3.

In the first and second reactor, the reaction selectivity with respectto hydrogen peroxide is 98% molar with a conversion of 96%, in the thirdreactor there is a selectivity of 80% molar and a conversion of 95%. Theflash columns substantially operate under the same operating conditionsand discharge, at the head, streams in vapour phase essentiallyconsisting of non-reacted olefin, olefin oxide, inert products, forexample aliphatic hydrocarbons such as propane, and solvent vapours. Atthe bottom, the columns discharge streams in liquid phase with adifferentiated composition, which for C1 and C2 are partly recycled tothe respective synthesis reactors R1 and R2.

The vapours at the head of columns C1-C2-C3 are fed to a distillationcolumn C4 to recover the non-reacted olefin at the head. The latter isrecycled to the synthesis of the olefin oxide after partial eliminationof the inert products. The vapours coming from the vents of reactorsR1-R2-R3, are also fed to the column C4.

The temperature at the bottom of the column C4 must not exceed 80° C.with residence times in the order of 1 minute; this is to avoiddegradation of the olefin oxide.

Whereas the streams at the bottom of the distillation columns C1 and C2still contain significant quantities of hydrogen peroxide, and aretherefore recycled to the synthesis of the olefin oxide, the stream atthe tail of the column C3 is substantially without H₂O₂ and essentiallyconsists of solvent, water and reaction by-products.

This stream is fed to a decomposition section of the residual hydrogenperoxide R4 consisting of one or more fixed bed tubular reactorsarranged in series.

The hydrogen peroxide decomposition reaction is exothermic and takesplace in liquid phase at about 80-90° C., with a residence time rangingfrom 1 to 10 minutes, preferably from 2 to 5 minutes.

Examples of catalysts used in the decomposition reaction consist ofmetals of group VIII or their oxides. The carriers are selected fromthose of the known art and indicated above.

The mixture leaving R4 is fed to a phase separator V4 which separatesthe oxygen generated from the decomposition of the hydrogen peroxide andthe dilution inert product, preferably nitrogen, charged downstream ofthe reactor R4 to maintain the solvent/oxygen mixture released in theflash column below the lower flammability limit.

The solvent-oxygen-inert product mixture leaving V4, is then condensedin two condensers in series to recover the solvent, whereas thenon-condensable products (oxygen and inert product with traces ofsolvent) are discharged.

The liquid phase leaving R4 and the liquid mixture leaving V4 are fed tothe distillation column C6-A and treated as described above.

The condensation heat recovered at the head of the column C6-A can beused to supply all the reboiling units present in the process. In thiscase, the pressure of the column is kept at a suitable value for thispurpose.

A liquid stream rich in olefin oxide is extracted from the bottom of thedistillation column C4, and is sent to a purification section C5.

The latter consists of two columns in series due to the high number ofplates and separates, at the head, residual vapours still present(non-reacted olefin and inert gases), at the bottom, a liquid streamcontaining solvent and olefin oxide (recycled to the distillation columnC3) and, laterally, a liquid stream consisting of olefin oxide with acommercial purity (>99.8%).

The vapours extracted from the head of the purification column C5 maystill contain significant quantities of olefin oxide and are recycledupstream of the distillation column C4.

Operating with the process of the present invention, the epoxidationcatalyst, after 1000 hours, does not show any sign of deterioration andthe productivity and reaction selectivity are high.

The process for the preparation of olefin oxides can be betterunderstood by referring to the block schemes of FIG. 1, which representsan illustrative but non-limiting embodiment.

With reference to FIG. 1, the olefin, for example propylene, is fed inparallel to the reactors R1-R2-R3 with lines (2)-(11)-(21). Thebuffering agent is fed to the reactors R1-R2-R3 parallelly with lines(T1)-(T2)-(T3), whereas half of the recycled solvent with the hydrogenperoxide (4) is fed to the reactor R1 (4A) and the other half to R2(4B). Possible solvent losses in the integrated production cycle arereplaced by means of “make-up” line (3) which enters with the feeding ofcolumn C6-A.

Propylene Oxide Synthesis Reaction

The filtered liquid reaction product leaving the first reactor R1 is fedwith line (6) to the first distillation column C1 from whose head thepropylene oxide produced and non-reacted propylene (7), in vapour phase,are recovered, and from the bottom, a liquid stream (8) still containinghydrogen peroxide, a part of (8) is fed to the reactor R3 and theremaining stream (8A) is recycled to the reactor R1 to dilute thehydrogen peroxide to the desired concentration.

The filtered liquid reaction product leaving the second reactor R2 isfed with line (9) to the second distillation column C2 from whose headthe propylene oxide produced and non-reacted propylene (12), in vapourphase, are recovered, and from the bottom, a liquid stream (13) stillcontaining hydrogen peroxide, a part of (13) is fed to the reactor R3and the remaining stream (13A) is recycled to the reactor R2 to dilutethe hydrogen peroxide to the desired concentration.

The filtered liquid reaction product leaving the second reactor R3 isfed with line (14) to the third distillation column C3 from whose headthe propylene oxide produced and non-reacted propylene (16), in vapourphase, are recovered, and from the bottom, a liquid stream (15) stillcontaining hydrogen peroxide, fed to the reactor system R4 (the systemR4 refers to the reactor R4 itself, a phase separator V4 and twocondensers in series E421/E422 on the vapour phase leaving V4).

The liquid reaction product leaving the system R4 is fed to the columnC6-A (18), the gaseous product vented into the atmosphere containingoxygen, nitrogen and traces of methanol is represented by line (17). Thediluting nitrogen is fed to the system R4 with line (AZ).

Recovery of the Solvent

The liquid product leaving the reactor system R4, without hydrogenperoxide and essentially consisting of solvent, water and by-products,is fed with line (18) to the solvent recovery section consisting in thisparticular case of a series of distillation columns C6 A-B-C. Water andthe reaction by-products (24) are discharged from the bottom of C6-A. Atthe head of C6-A, the solvent (23) is recovered and sent to the columnC6-B. At about ⅔ of the height of C6-A an acid solution (A1) is fed,which blocks the nitrogenated compounds present in vapour phase. Thehead of the column C6-B consisting of light compounds (methyl formiate,dimethoxymethane) present in the methanol at the inlet of C6-A, at aconcentration of 1-2% by weight of methanol, is fed to the column C6-C.The light concentrated products (6-8% by weight) leave the head of thecolumn C6-C with the flushing stream (31). The bottom products ofcolumns C6-B and C6-C when joined (33), form the methanol recycled tothe synthesis reaction of hydrogen peroxide.

Recovery of the Propylene Oxide

The streams (7), (12) and (16), together with the vented products of thesynthesis reactors, consist of non-reacted propylene, propylene oxideand solvent; they are fed, by means of the compressor K1, to thedistillation column C4. The propylene is separated at the head of thecolumn C4 together with the inert products (27)+(25). The inertproducts, such as propane, are inserted into the cycle together withfresh propylene (5). To prevent there being an accumulation of inertproducts in the production cycle, a part of the stream of propylenerecycled to the reactors, is flushed (25).

A stream rich in propylene oxide (28) is recovered at the bottom of thecolumn C4 and is fed to the purification section of propylene oxide, inthis particular case consisting of a distillation column C5 (in twosections). A stream in vapour phase (29) still containing traces ofnon-reacted propylene and propylene oxide is recovered at the head ofthe column C5; this stream is recycled by means of the compressor K1 tothe column C4. A liquid stream (26) containing propylene oxide andsolvent is extracted from the bottom of the column C5 and is sent backto the column C3.

The propylene oxide with a commercial purity is extracted from thecolumn C5 as a lateral cut (30).

Synthesis Reaction of Hydrogen Peroxide

The stream of distilled methanol (33) coming from the propylene oxidesynthesis section goes to the hydrogen peroxide synthesis section.

A stream (35) of an aqueous solution of HBr (halogenated promoter) and astream (36) of an aqueous solution of H₂SO₄ (acid promoter) are added tothe stream (33); the pump P1 sends the mixture obtained (37) to thehydrogen peroxide synthesis reactor R5 at a pressure of 100 bars. Thestreams (39)-(40)-(41) of hydrogen, oxygen and nitrogen, respectively,are sent by means of the compressor K2 to the reactor R5 at 100 bars.The ventilator K3 recycles the non-reacted gases from the top of thereactor into the reaction medium. The stream (44), consisting of thereaction products hydrogen peroxide and water, the methanol solvent andreaction gases dissolved at 100 bars, is fed to the flash column F1 atlow pressure. The vapour phase leaving F1, after condensation (45),feeds the separation column C7 fed at the head with water (48). Thegases at the head C7 (46) are flushed from the cycle, the stream (47) atthe bottom of the column C7 containing traces of methanol and water issent to a biological treatment system. The gases of the top of thereactor removed for analysis with the on-line analyzer An, are also sentto the flash column F1.

The liquid stream (4) leaving F1 consists of hydrogen peroxide (7%weight), water and methanol. Said stream forms the feeding stream to thepropylene oxide synthesis

Compared with the known methods, the process described above allowsepoxides to be obtained with a high productivity over a period of timeand a high selectivity, using a method which can be easily applied on anindustrial scale and with the possibility of operating in continuous.

The following operative example is provided for illustrative purposesand does not limit the scope of the invention.

EXAMPLE 1

The procedure is adopted according to FIG. 1 to produce propylene oxidestarting from:

-   -   a stream deriving from a steam cracking plant consisting of        99.5% by weight of propylene and 0.05% by weight of propane;    -   a gaseous stream containing hydrogen, oxygen and nitrogen,        characterized in that the concentration of hydrogen is lower        than 4.5% by volume and the concentration of oxygen is lower        than 21% by volume, the complement to 100 being nitrogen;    -   make-up methanol;    -   an acid promoter H₂SO₄ (200 mg per kg of liquid medium) and a        halogenated promoter HBr (6 mg per kg of liquid medium) fed to        the methanol stream at the inlet of R5;    -   a buffering agent consisting of an aqueous solution of NH₄OH,        fed to the stream of methanol at the inlet of reactors R1-R2-R3        in such a quantity as to buffer the pH of the reaction mixture        to a value of 6.5 (present in the liquid stream in the feeding        to R1-R2-R3 in a concentration of 80 ppm); a reinforced glass        pH-meter inserted in the reaction stream, is used;    -   a diluted solution containing sulfuric acid (about 10-50 mg/kg        of sulfuric acid with respect to the total stream (18), fed to        the column C6-A to obtain a distillation under acid conditions        of the methanol recycled to R5.

The titanium silicalite catalyst, of the type described in patent U.S.Pat. No. 4,937,216, is present in the reactors R1, R2 and R3 in aconcentration of 6% by weight with respect to the slurry.

The catalyst bed of the decomposer R4, in pellets with an active phaseof 15%, is charged in volume excess to guarantee exhaustion of thehydrogen peroxide.

The heterogeneous catalyst based on palladium and platinum is kept indispersion in the liquid reaction medium at 1% by weight in R5.

Table 1 enclosed (3 pages) indicates the balances and composition of thesingle streams.

TABLE 1-A Streams 2 3 4 4A Components (kg/h) (%) (kg/h) (%) (kg/h) (%)(kg/h) (%) Propylene 411.63 93.95 Propane 26.50 6.05 Propylene oxide(PO) Methanol (MeOH) 0.00 0.01 7.70 100 2069.10 89.68 1034.55 89.68Water (H2O) 0.00 0.00 78.22 3.39 39.11 3.39 Hydrogen peroxide (H2O2)0.00 0.00 0.00 0.00 160.00 6.93 80.00 6.93 Methoxypropanol 0.00 0.000.00 0.00 0.00 0.00 0.00 0.00 1,2propandiol 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 FLOW RATE 438.1 100 7.70 100 2307.3 100 1153.7 100Temperature −14.50 35.00 35.00 35.00 Pressure 16.00 16.00 16.00 16.00Streams 4B 5 6 7 Components (kg/h) (%) (kg/h) (%) (kg/h) (%) (kg/h) (%)Propylene 207.3 99.50 318.2 11.92 318.2 60.25 Propane 1.035 0.50 26.50.99 26.5 5.03 Propylene oxide (PO) 128.4 4.81 128.4 24.31 Methanol(MeOH) 1034.55 89.68 2067.9 77.44 55.0 10.41 Water (H2O) 39.11 3.39118.7 4.45 0.0 0.00 Hydrogen peroxide (H2O2) 80.00 6.93 4.8 0.18 0.00.00 Methoxypropanol 0.00 0.00 4.9 0.18 0.0 0.00 1,2propandiol 0.00 0.001.0 0.04 0.0 0.00 FLOW RATE 1153.7 100 208.3 100 2670.5 100 528.2 100Temperature 35.00 37.50 50.00 36.60 Pressure 16.00 16.00 13.00 1.80Streams 17 18 8-A 13-A Components (kg/h) (%) (kg/h) (%) (kg/h) (%)(kg/h) (%) Propylene Propane Propylene oxide (PO) 0.0 0.00 0.0 0.00Methanol (MeOH) 0.6 27.46 2065.2 92.25 1034.5 96.04 1034.54 96.04 Water(H2O) 0.003 0.13 162.5 7.26 39.11 3.63 39.11 3.63 Hydrogen peroxide(H2O2) 0.0 0.00 1.6 0.15 1.60 0.15 Methoxypropanol 9.08 0.41 1.6 0.151.63 0.15 1,2propandiol 1.92 0.09 0.343 0.03 0.34 0.03 Oxygen 0.15 6.61NH4OH H2SO4 Nitrogen 1.5 65.80 0.000 0.00 FLOW RATE 2.3 100 2238.7 1001077.2 100 1077.2 100 Temperature −15.00 67.30 84.30 40.00 Pressure 1.101.20 16.00 16.00 Streams 21 22 23 24 Components (kg/h) (%) (kg/h) (%)(kg/h) (%) (kg/h) (%) Propylene 202.6 93.95 0.00 0.00 Propane 13.0 6.050.00 0.00 Propylene oxide (PO) 0.001 0.00 0.00 0.00 Methanol (MeOH)2065.87 92.25 2072.9 97.04 0.0 0.00 Water(H2O) 162.49 7.26 63.28 2.9699.2 90.02 Hydrogen peroxide (H2O2) 0.00 0.00 Methoxypropanol 9.08 0.410.00 0.00 9.08 8.24 1,2propandiol 1.92 0.09 1.92 1.74 Oxygen 0.15 0.007NH4OH H2SO4 Nitrogen 0.02 0.00 FLOW RATE 215.6 100 2239.5 100 2136.2 100110.2 100 Temperature −1450 89.8 87.00 128.60 Pressure 16.00 10 2.502.66

TABLE 1-B Streams 8 9 10 11 12 Components (kg/h) (%) (kg/h) (%) (kg/h)(%) (kg/h) (%) (kg/h) (%) Propylene 0.0 0.00 318.2 11.92 0.0 0.00 411.6393.95 318.2 60.25 Propane 0.0 0.00 26.5 0.99 0.0 0.00 26.50 6.05 26.55.03 Propylene oxide (PO) 0.000 0.00 128.4 4.81 0.0 0.00 128.4 24.31Methanol (MeOH) 2012.9 93.96 2067.9 77.44 1956.8 91.86 55.0 10.41 Water(H2O) 118.7 5.54 118.7 4.45 159.2 7.47 0.0 0.00 Hydrogen peroxide (H2O2)4.8 0.22 4.8 0.18 6.4 0.30 0.0 0.00 Methoxypropanol 4.9 0.23 4.9 0.186.5 0.31 0.0 0.00 1,2propandiol 1.0 0.05 1.0 0.04 1.4 0.06 0.0 0.00 FLOWRATE 2142.4 100 2670.5 100 2130.3 100 438.1 100 528.2 100 Temperature84.30 50.00 30.00 −14.50 50.00 Pressure 1.94 13.00 16.00 16.00 16.00Streams 13 14 15 16 Components (kg/h) (%) (kg/h) (%) (kg/h) (%) (kg/h)(%) Propylene 0.0 0.00 195.2 8.32 0.0 0.00 196.2 55.70 Propane 0.0 0.0012.9 0.55 0.000 0.00 12.9 3.68 Propylene oxide (PO) 0.0 0.00 8.30 0.350.00 0.00 51.6 14.71 Methanol (MeOH) 2012.9 93.96 1955.9 83.37 2065.8792.25 90.0 25.68 Water (H2O) 118.7 5.54 162.3 6.92 162.32 7.25 0.76 0.22Hydrogen peroxide (H2O2) 4.8 0.22 0.3 0.01 0.3 0.01 0.0 0.00Methoxypropanol 4.9 0.23 9.1 0.39 9.1 0.41 0.0 0.00 1,2propandiol 1.00.05 1.9 0.08 1.9 0.09 0.0 0.00 FLOW RATE 2142.4 100 2345.9 100 2239.5100 350.4 100 Temperature 50.00 37.80 88.20 40.00 Pressure 13.00 1.802.01 1.10 Streams 25 26 27 28 29 Components (kg/h) (%) (kg/h) (%) (kg/h)(%) (kg/h) (%) (kg/h) (%) Propylene 10.000 90.62 1028.8342 93.98 3.002.01 2.9910 2.72 Propane 1.035 9.38 65.9410 6.02 0.29 0.19 0.2850 0.26Propylene oxide (PO) 43.3 17.72 0.00 0.00 106.7210 97.02 Methanol (MeOH)200.0 81.96 145.00 97.28 0.0020 0.00 Water (H2O) 0.77 0.32 0.77 0.510.0010 0.00 Hydrogen peroxide (H2O2) 0.00 0.00 Methoxypropanol 0.00 0.001,2propandiol Oxygen NH4OH H2SO4 Nitrogen 0.0000 0.00 FLOW RATE 11.0 100244.0 100 1094.8 100 149.1 100 110.0 100 Temperature −14.30 63.40 −14.5075.30 37.60 Pressure 3.80 1.68 3.80 3.88 1.20 Streams 30 T 1-2-3 A1 AZ33 Components (kg/h) (%) (%) (%) (kg/h) (%) (kg/h) (%) Propylene 0.0090Propane 0.0010 Propylene oxide (PO) 265.114 99.99 Methanol (MeOH) 0.01202068.9 97.03 Water (H2O) 0.0020 90.00 90.00 63.28 2.97 Hydrogen peroxide(H2O2) Methoxypropanol 1,2propandiol Oxygen NH4OH 10.00 H2SO4 10.00Nitrogen 1.50 100.0 FLOW RATE 265.1 100 100 100 1.5 100 2132.2 100Temperature 39.10 30.00 30.00 30.00 Pressure 1.22 16.00 16.00 16.00

TABLE 1-C Streams 31 35 36 37 38 40 41 Components (kg/h) (%) (kg/h) (%)(kg/h) (%) (kg/h) (%) (kg/h) (%) (kg/h) (%) (kg/h) (%) Hydrogen Oxygen182.9 100 Nitrogen 43.9 100.00 Methanol 4.00 100.00 2068.94 96.88 99.84(MeOH) Water (H2O) 0.26 96.30 2.61 85.02 66.15 3.10 0.14 Hydrogen 0.000.00 peroxide (H2O2) HBr 0.01 3.70 0.01 0.00 0.0 0.00 H2SO4 0.46 14.980.46 0.02 0.5 0.02 FLOW RATE 4.0 100 0.27 100 3.1 100 2135.6 100 0.5 100182.9 100 43.9 100 Temperature 35.00 35.00 35.00 35.00 35.00 −180.0030.00 Pressure 2.50 2.50 2.50 2.50 100.00 4.00 3.10 Streams 42 43 44 4546 48 47 Components (kg/h) (%) (kg/h) (%) (kg/h) (%) (kg/h) (%) (kg/h)(%) (kg/h) (%) (kg/h) (%) Hydrogen 12.6 5.25 0.00 1.30 0.0 0.00 0.0 0.060.0 0.06 Oxygen 182.9 76.41 0.00 6.10 7.2 0.31 7.2 14.13 7.2 14.15Nitrogen 43.9 18.34 0.00 92.60 43.9 1.86 43.9 85.71 43.9 85.80 Methanol2069.1 87.71 0.05 0.10 0.1 0.05 (MeOH) Water (H2O) 78.2 3.32 100.00100.00 100.0 99.95 Hydrogen 160.0 6.78 peroxide (H2O2) HBr 0.01 0.00H2SO4 0.46 0.02 FLOW RATE 239.4 100 0.0 100 2359.0 100 51.2 100 51.2 100100.0 100.0 100.1 100 Temperature 30.00 30.00 30.00 30.00 30.00 30.0030.00 Pressure 100.00 100.00 100.00 1.50 1.00 1.00 1.00

1. An integrated process for the continuous production of epoxides bythe direct oxidation of an olefin with hydrogen peroxide whichcomprises: (a) preparing an alcoholic or hydro-alcoholic solution ofhydrogen peroxide in a concentration of over 3% by weight, using agaseous stream containing hydrogen, oxygen and an inert gas, in thepresence of a bimetallic catalyst based on palladium and platinum asactive components; (b) putting the alcoholic or hydro-alcoholic solutionof hydrogen peroxide obtained in step (a) in contact with an olefin anda buffering agent, in the presence of an epoxidation catalyst suspendedin the reaction solvent, in order to obtain a reaction mixturecontaining the epoxide corresponding to the olefin, water and thealcoholic solvent; (c) treating the alcoholic stream leaving step (b),after separation of the epoxide, in order to eliminate the nitrogenatedcompounds present; (d) feeding the alcoholic solvent obtained in (c) tostep (a).
 2. The process according to claim 1, wherein in step (c) thetreatment of the alcoholic stream is effected by distilling the solventtogether with an aqueous or diluted hydro-alcoholic solution containingsulfuric acid in a quantity of about 10-50 mg/kg of sulfuric acid withrespect to the total stream, or by treating the distilled solvent withactivated carbons, sulfonic resins or sulfonated carbons.
 3. The processaccording to claim 1, which comprises a further step (e), wherein theraw hydro-alcoholic mixture of the flash column bottom is used fordiluting the alcoholic or hydro-alcoholic solution of hydrogen peroxideleaving step (a) to the value required by the epoxidation plant.
 4. Theprocess according to claim 1, wherein step (a) for the production incontinuous of alcoholic or hydro-alcoholic solutions of hydrogenperoxide comprises: (a′) feeding to a reactor, containing a catalystbased on palladium and platinum, heterogeneous and kept in dispersion ina liquid reaction medium: (i) a liquid stream consisting of an alcoholor an alcohol-water mixture with a prevalent alcoholic content,containing an acid promoter and a halogenated promoter: (ii) a gaseousstream containing hydrogen, oxygen and an inert gas, characterized inthat the concentration of hydrogen is lower than 4.5% by volume and theconcentration of oxygen is lower than 21% by volume, the complement to100 being an inert gas; (b′) removing from the reactor: (iii) a liquidstream essentially consisting of the stream (i) and also containing thehydrogen peroxide and water produced by the reaction, characterized inthat the concentration of hydrogen peroxide is higher than 3% by weight;and (iv) a gaseous stream essentially consisting of non-reacted hydrogenand oxygen and the inert gas.
 5. The process according to claim 1,wherein the catalyst in step (a′) contains palladium in a quantityranging from 0.1 to 3% by weight and platinum in a quantity ranging from0.01 to 1% by weight, with an atomic ratio platinum and palladiumranging from 1/500 to 100/100.
 6. The process according to claim 5,wherein the catalyst contains a quantity of palladium ranging from 0.4to 2% by weight and a quantity of platinum ranging from 0.02 to 0.5% byweight, with an atomic ratio platinum and palladium ranging from 1/200to 20/100.
 7. The process according to claim 5, wherein the catalyst, inaddition to palladium and platinum, contains another metal selected fromthose of group VIII or IB.
 8. The process according to claim 7, whereinthe metal is ruthenium, rhodium, iridium or gold.
 9. The processaccording to claim 4, wherein the catalyst is prepared by dispersing theactive components on an inert carrier by means of precipitation and/orimpregnation.
 10. The process according to claim 9, wherein the inertcarrier is selected from silica, alumina, silica-alumina, zeolites,activated carbon and activated carbon functionalized with sulfonicgroups.
 11. The process according to claim 10, wherein the carrier is anactivated carbon selected from those of fossil or natural originderiving from wood, lignite, peat or coconut and having a surface areahigher than 300 m²/g.
 12. The process according to claim 11, wherein thecarrier is an activated carbon having a surface area which can reach avalue of 1400 m²/g.
 13. The process according to claim 12, wherein thecarrier is an activated carbon with a surface area higher than 600 m²/g.14. The process according to claim 11, wherein the activated carbon hasa low ash content.
 15. The process according to claim 4, wherein thecatalyst is dispersed in the reaction medium at a concentration rangingfrom 0.1 to 10% by weight.
 16. The process according to claim 15,wherein the catalyst is dispersed in the reaction medium at aconcentration ranging from 0.3 to 3% by weight.
 17. The processaccording to claim 4, wherein the liquid stream (i) consists of analcohol or mixture of C₁-C₄ alcohols or a mixture of said alcohols withwater with an alcoholic content higher than 50%.
 18. The processaccording to claim 17, wherein the alcohol is methanol.
 19. The processaccording to claim 17, wherein the mixture is a mixture of methanol andwater containing at least 70% by weight of methanol.
 20. The processaccording to claim 4, wherein the halogenated promoter is a substancecapable of generating halogen ions in the liquid reaction medium. 21.The process according to claim 20, wherein the halogenated promoter isselected from substances capable of generating bromide ions such ashydrobromic acid and its salts soluble in the reaction medium, such asalkaline bromides.
 22. The process according to claim 21, wherein thepromoter is hydrobromic acid.
 23. The process according to claim 4,wherein the concentration of the halogenated promoter ranges from 0.1 to50 mg per kg of solution.
 24. The process according to claim 23, whereinthe concentration of the halogenated promoter ranges from 1 to 10 mg perkg of solution.
 25. The process according to claim 4, wherein the acidpromoter is selected from substances capable of generating H⁺ hydrogenions in the reaction medium.
 26. The process according to claim 25,wherein the acid promoter is selected from inorganic acids such assulfuric, phosphoric, nitric acid or organic acids such as sulfonicacids.
 27. The process according to claim 26, wherein the acid promoteris sulfuric acid or phosphoric acid.
 28. The process according to claim4, wherein the concentration of acid promoter ranges from 0 to 1000 mgper kg of solution.
 29. The process according to claim 28, wherein theconcentration of acid promoter ranges from 10 to 500 mg per kg ofsolution.
 30. The process according to claim 4, wherein in the gaseousstream (ii) the concentration of hydrogen ranges from 2% to 4% by volumeand the concentration of oxygen ranges from 6% to 18% by volume, thecomplement to 100 being an inert gas selected from nitrogen, helium andargon.
 31. The process according to claim 30, wherein the inert gas isnitrogen.
 32. The process according to claim 4, wherein in the gaseousstream (ii) the oxygen can be supplied using as raw material pure orsubstantially pure oxygen, enriched air, containing from 21 to 90% ofoxygen or air, the composition of the, stream then being brought to thedesired value by the addition of a suitable concentration of inert gas.33. The process according to claim 4, wherein the liquid stream (iii)leaving the reactor has a concentration of hydrogen peroxide rangingfrom 4% to 10% by weight.
 34. The process according to claim 4, whereinthe liquid stream (iii) is separated from the catalyst by means offiltration.
 35. The process according to claim 34, wherein thefiltration is carried out using filters situated inside the reactor orexternally by means of tangential filtration.
 36. The process accordingto claim 4, wherein the gaseous stream (iv) leaving the reactor,essentially consisting of non-reacted hydrogen and oxygen and the inertgas, contains a volume concentration of hydrogen equal to or lower than2% and a volume concentration of oxygen lower than 18%.
 37. The processaccording to claim 36, wherein the gaseous stream (iv) leaving thereactor, contains a volume concentration of hydrogen ranging from 0.5 to1.5% by volume and a volume concentration of oxygen ranging from 6 to12%.
 38. The process according to claim 4, wherein the gaseous stream(iv) leaving the reactor is recycled to the feeding to the reactor,after flushing from the system the fraction necessary for eliminatingthe quantity of inert gas charged in excess with the feeding and theaddition of H₂ and O₂ used up in the process.
 39. The process accordingto claim 4, wherein the gaseous stream (iv) leaving the reactor is fedto one or more subsequent reactors operating analogously to thatdescribed in claim 4, after adding each time a quantity of hydrogen andoxygen essentially equal to that used up by the reaction which takesplace in the single reactors.
 40. The process according to claim 4,wherein the reaction is carried out at a temperature ranging from −10 to60° C.
 41. The process according to claim 40, wherein the temperatureranges from 0 to 40° C.
 42. The process according to claim 4, whereinthe reaction is carried out at a total pressure ranging from 1 to 300bars.
 43. The process according to claim 42, wherein the total pressureranges from 40 to 150 bars.
 44. The process according to claim 4,wherein the reactor is a reactor suitable for operating in continuousand carrying out the reaction in a triphasic system, obtaining aneffective contact between gaseous phase, liquid phase and the catalystkept in suspension.
 45. The process according to claim 4, wherein thereactor is selected from stirred reactors, bubble reactors or gas-liftreactors with internal or external circulation.
 46. The processaccording to claim 4, wherein the residence time of the liquid medium inthe reactor ranges from 0.05 to 5 hours.
 47. The process according toclaim 46, wherein the residence time of the liquid medium in the reactorranges from 0.1 to 2 hours.
 48. The process according to claim 1,wherein step (b) for the production of epoxides comprises: (1) feedingthe liquid stream (iii) leaving step (a) to a reaction unit consistingof one or more reactors containing the epoxidation catalyst suspended inthe reaction solvent together with the olefin, hydrogen peroxide and abuffering agent; (2) feeding the filtered liquid product leaving thereaction unit is fed to a distillation unit consisting of one or morestripping (flash) columns, one for each reactor of the reaction unit, toobtain a product at the head essentially consisting of olefin oxide andnon-reacted olefin and a product at the bottom essentially consisting ofsolvent, non-reacted hydrogen peroxide, water and reaction by-products;(3) feeding the product at the bottom of the distillation unit to adecomposition unit R4 consisting of one or more reactors situated inseries containing a supported decomposition catalyst having the functionof decomposing the residual hydrogen peroxide into O₂ and H₂O; (4)feeding the mixture leaving the decomposition unit R4, essentiallyconsisting of solvent, oxygen and water, together with an inert gas to aphase separator V4 to obtain, at the head, a gaseous phase containingoxygen, inert gas and traces of solvent and, at the bottom, a liquidphase consisting of solvent, water and reaction by-products; (5) feedingthe gaseous phase leaving V4 to a condensation system consisting of oneor more condensers in series for the recovery of the residual solvent,whereas the non-condensable compounds (oxygen and inert gas with tracesof solvent) are discharged; (6) feeding the solvent leaving thecondensation system and the liquid phase leaving V4 to the distillationcolumn C6-A to obtain, at the head, the solvent which is recycled to thereaction unit (a), and a product, at the bottom, essentially consistingof reaction water and that charged with the hydrogen peroxide, reactionby-products and traces of solvent, which is discharged; (7) feeding theproduct at the head of the stripping column(s) together with the ventproducts of the reactors to a distillation column C4 to obtain aproduct, at the head, consisting of non-reacted olefin, recycled to thereaction unit, and a product, at the bottom essentially consisting ofolefin oxide; (8) feeding the product at the bottom of the distillationcolumn C4 to a purification system C5 to recover the residual olefin,recycled to the reaction unit, a liquid phase essentially consisting ofsolvent, recycled to the flash column(s), and the olefin oxide with acommercial purity.
 49. The process according to claim 48, wherein instep (6) the solvent leaving the condensation system and the liquidphase leaving R4 are fed to the distillation column C6-A together with adiluted aqueous or hydro-alcoholic solution containing 10-50 mg/kg ofsulfuric acid with respect to the total stream.
 50. The processaccording to claim 49, wherein the solvent leaving the condensationsystem and the liquid phase leaving V4 are fed towards the bottom of thedistillation column C6-A, whereas the acid solution is fed to a heightequal to about ⅔ of the column itself.
 51. The process according toclaim 49, wherein the solvent leaving the head of the column C6-A is fedto a column C6-B, in order to separate the light products at the head,whereas the purified solvent is separated at the bottom.
 52. The processaccording to claim 51, wherein the stream at the head of the column C6-Bis sent to a distillation column C6-C, to recover, at the bottom, thesolvent without light products, recycled to the hydrogen peroxidesynthesis reaction, and a concentrated stream of light products, at thehead.
 53. The process according to claim 48, wherein in step (6) thesolvent at the head of the column C6-A is recycled to the hydrogenperoxide synthesis reaction after treatment with activated carbons,sulfonic resins or sulfonated carbons.
 54. The process according toclaim 48, wherein the reaction unit consists of three reactors R1, R2and R3.
 55. The process according to claim 1, wherein in step (b) theolefin is selected from those having general formula (I)

wherein: R₁, R₂, R₃ and R₄, the same or different, can be hydrogen, analkyl radical with from 1 to 20 carbon atoms, an aryl radical, alkylarylradical with from 7 to 20 carbon atoms, a cyclo-alkyl radical with from6 to 10 carbon atoms, an alkylcyclo-alkyl radical with from 7 to 20carbon atoms.
 56. The process according to claim 55, wherein in thecompounds having formula (I), the radicals R_(1, R) ₂, R₃ and R₄, canform, in pairs, saturated or unsaturated rings and can contain halogenatoms, nitro, nitrile, sulfonic and relative ester groups, carbonyl,hydroxyl, carboxyl, thiol, amine and ether groups.
 57. The processaccording to claim 55, wherein olefins having formula (I) are: ethylene,propylene, allyl chloride, allyl alcohol, butenes, pentenes, hexenes,heptenes, octene-1, 1-tridecene, mesityl oxide, isoprene, cyclo-octene,cyclo-hexene or bicyclic compounds such as norbornenes, pinenes.
 58. Theprocess according to claim 57, wherein the olefin is propylene.
 59. Theprocess according to claim 58, wherein the propylene has a purity ofover 70%.
 60. The process according to claim 59, wherein the propyleneis available as a stream from steam cracking with a minimum purity of96%, the remainder consisting of propane and typical C₃ impurities. 61.The process according to claim 48, wherein the olefin fed to thereaction unit consists of fresh olefin, recycled olefin or theirmixtures.
 62. The process according to claim 61, wherein, beforeentering the reaction unit, the fresh olefin is purified in thedistillation column C4.
 63. The process according to claim 48, whereinthe liquid stream (iii) is fed to step (1) so as to have a molar ratioolefin/H₂O₂ ranging from 10:1 to 1:10.
 64. The process according toclaim 63, wherein the molar ratio olefin/H₂O₂ ranges from 6:1 to 1:1.65. The process according to claim 48, wherein the solvent used in theepoxidation reaction consists of an alcohol or mixture of C₁-C₄ alcoholsor a mixture of said alcohols with water with an alcoholic contenthigher than 50%.
 66. The process according to claim 65, wherein thealcohol is methanol.
 67. The process according to claim 65, wherein themixture is a mixture of methanol and water containing at least 70% byweight of methanol.
 68. The process according to claim 48, wherein thebuffering agent is selected from ammonia, ammonium acetate, ammoniumformiate or a system consisting of a nitrogenated base and a saltthereof with an organic or inorganic acid.
 69. The process according toclaim 48, wherein the buffering agent is fed in continuous with one ofthe reagent streams fed to the epoxidation reactor, in such a quantityas to maintain the pH of the reaction mixture, measured under operativeconditions, at a value higher than
 5. 70. The process according to claim69, wherein the pH of the reaction mixture is maintained at a valueranging from 5.5 to
 8. 71. The process according to claim 1, wherein theepoxidation catalyst of step (b) is selected from titanium-silicaliteswith an MFI structure, titanium-silicalites with a MEL or intermediateMFI/MEL structure or beta zeolites containing titanium and having a BEAstructure.
 72. The process according to claim 71, wherein the catalystis selected from titanium-silicalites having general formula (II): xTiO₂·(1−x)SiO₂ wherein x ranges from 0.0001 to 0.04.
 73. The processaccording to claim 72, wherein in the titanium silicalite, part of thetitanium is substituted by metals selected from boron, aluminum, iron orgallium.
 74. The process according to claim 1, wherein the catalyst canbe used in the form of powder, pellets, microspheres, extruded or otherconvenient physical forms.
 75. The process according to claim 74,wherein the catalyst can be used in a combination with a ligand (co-gel)or a carrier selected from silica, alumina, silica-alumina, zeolites oractivated carbon.
 76. The process according to claim 1, wherein thequantity of catalyst used in the epoxidation reaction ranges from 1 to15% by weight with respect to the reaction mixture.
 77. The processaccording to claim 76, wherein the quantity of catalyst ranges from 4 to10% by weight with respect to the reaction mixture.
 78. The processaccording to claim 1, wherein the epoxidation reaction is carried out ata temperature ranging from 20 to 150° C.
 79. The process according toclaim 78, wherein the temperature ranges from 40 to 100° C.
 80. Theprocess according to claim 79, wherein the temperature ranges from 55 to90° C.
 81. The process according to claim 54, wherein the reactors R1and R2 operate at a temperature of 55-75° C. and a pressure of 13 bars,and the reactor R3 operates at a temperature of 70-90° C. and a pressureof 8 bars.
 82. The process according to claim 48, wherein thedecomposition reaction of residual hydrogen peroxide is carried out at atemperature ranging from 80 to 90° C., with a residence time rangingfrom 1 to 10 minutes.
 83. The process according to claim 82, wherein theresidence time ranges from 2 to 5 minutes.
 84. The process according toclaim 48, wherein the catalysts used in the decomposition reaction ofresidual hydrogen peroxide consist of metals of group VIII or theiroxides.
 85. The process according to claim 48, wherein the epoxidationreactors are selected from stirred reactors, bubble reactors, gas-liftreactors with internal or external circulation or CSTR (ContinuousStirred Tank Reactors) or PFR (Plug Flow Reactors).
 86. The processaccording to claim 54, wherein the reactors R1, R2, R3 are of theisotherm CSTR type.
 87. The process according to claim 48, wherein thedecomposition reactor R4 consists of one or more fixed bed tubularreactors arranged in series.
 88. The process according to claim 48,wherein the stripping columns operate under the same operatingconditions and discharge, at the head, streams in vapour phaseessentially consisting of non-reacted olefin, olefin oxide, inertproducts and solvent vapour.
 89. The process according to claim 48,wherein the temperature at the bottom of the distillation column C4 doesnot exceed 80° C., with residence times in the order of 1 minute. 90.The process according to claim 48, wherein the purification column C5consists of two columns in series with a high number of plates andseparates, at the head, residual vapours still present, at the bottom, aliquid stream containing solvent and olefin oxide and, laterally, aliquid stream consisting of olefin oxide having a purity >99.8%.
 91. Theprocess according to claim 48, wherein the condensation heat recoveredat the head of the column C6 is used to supply all the reboiling unitspresent in the process.